CN101958347A - Nanostructure functional coating and device - Google Patents

Nanostructure functional coating and device Download PDF

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Publication number
CN101958347A
CN101958347A CN2010102365172A CN201010236517A CN101958347A CN 101958347 A CN101958347 A CN 101958347A CN 2010102365172 A CN2010102365172 A CN 2010102365172A CN 201010236517 A CN201010236517 A CN 201010236517A CN 101958347 A CN101958347 A CN 101958347A
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nanostructure
functional coating
article
substrate
reflecting layer
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CN101958347B (en
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L·察卡拉科斯
E·G·巴特菲尔德
A·M·斯里瓦斯塔瓦
B·A·科尔瓦尔
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General Electric Co
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/118—Anti-reflection coatings having sub-optical wavelength surface structures designed to provide an enhanced transmittance, e.g. moth-eye structures
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/02—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of crystals, e.g. rock-salt, semi-conductors
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/35—Non-linear optics
    • G02F1/3501—Constructional details or arrangements of non-linear optical devices, e.g. shape of non-linear crystals
    • G—PHYSICS
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    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/35—Non-linear optics
    • G02F1/353—Frequency conversion, i.e. wherein a light beam is generated with frequency components different from those of the incident light beams
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/35—Non-linear optics
    • G02F1/355—Non-linear optics characterised by the materials used
    • G02F1/3551—Crystals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0216—Coatings
    • H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0216—Coatings
    • H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0236—Special surface textures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
    • H01L31/055—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means where light is absorbed and re-emitted at a different wavelength by the optical element directly associated or integrated with the PV cell, e.g. by using luminescent material, fluorescent concentrators or up-conversion arrangements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/44—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the coatings, e.g. passivation layer or anti-reflective coating
    • H01L33/46—Reflective coating, e.g. dielectric Bragg reflector
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/35—Non-linear optics
    • G02F1/3501—Constructional details or arrangements of non-linear optical devices, e.g. shape of non-linear crystals
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/52—PV systems with concentrators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S977/00—Nanotechnology
    • Y10S977/70—Nanostructure
    • Y10S977/832—Nanostructure having specified property, e.g. lattice-constant, thermal expansion coefficient
    • Y10S977/834—Optical properties of nanomaterial, e.g. specified transparency, opacity, or index of refraction

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Abstract

In one aspect of the invention, a kind of article that comprise the nanostructure functional coating that is arranged on the substrate are described.This functional coating is characterised in that antireflection character and downward conversion character.Relevant photoelectric device is also described.

Description

Nanostructure functional coating and device
Technical field
In general, the present invention relates to be used to improve the coating of the optical surface of power conversion.More particularly, the present invention relates to be used for improve the coating of the power conversion of photoelectric device.The invention still further relates to the photoelectric device that utilizes this type coating.
Background technology
One of main focus in the photoelectric device field be improve energy conversion efficiency (otherwise from electromagnetic energy be converted to electric energy or).These devices can reduce owing to light loss suffers performance usually.Therefore, the research in the optical design of these devices comprises the absorption and the up/down transform light energy of light collection and seizure, Spectral matching.
A kind of potential light collection method is to reduce the light reflection by having the areflexia surface.For this reason, use antireflecting coating usually with appropriate index.But for example having, the availability of this type of material of the low-refraction between 1.0 (air) and 1.49 (glass) is very limited.
From current research as seen, compare with dense material, the nano-structured optical film with controlled porosity has low-down refractive index usually.For example, SiO 2The nanostructure porous membrane has about 1.08 refractive index usually, and this is far below SiO 2The value 1.46 of film.These individual layer antireflecting coating have only reduced reflectivity for normal incidence in limited spectral region.
In addition, because the charge carrier that generates by the high-energy photon thermalization mechanism of losing as the phonon in the crystal wherein, so these devices can suffer loss in efficiency.Energy causes each absorption photon only to generate an electron-hole pair greater than the absorption of the incident photon of the threshold energy that absorbs, and irrelevant with photon energy.During the thermalization of the electron-hole pair that is generated, the excessive power that surpasses the incident photon of threshold energy has just been wasted.Adopt some battery design of heterojunction Window layer to lose high-energy photon owing to the parasitism in the Window layer absorbs.Therefore, wish these high-energy photons (short wavelength) are converted to lower energy photon (long wavelength), lower energy photon can effectively absorb and be converted to collectable electric charge carrier in absorbed layer.
A kind of known method that overcomes light loss and relevant loss mechanism comprises high electromagnetic energy is longer wavelength from shorter wavelength " conversion downwards ".Since must avoid in the non-desired region/layer of photoelectric device, absorbing high-energy photon, thus can downward conversion layer be set on the surface of device, to be exposed to electromagnetic radiation.
Usually, the deposition of anti-reflecting layer and downward conversion layer comprises a plurality of treatment steps.Therefore, wish to produce improved coating system, so that satisfy the various performance requirements of photoelectric device with antireflection character and downward conversion character.In addition, the new coating system can provide the advantage that is easy to make.Wish very that also exploitation comprises the improved photoelectric device of this coating.
Summary of the invention
Embodiments of the invention provide a kind of article that comprise the nanostructure functional coating that is arranged on the substrate.Functional coating is characterised in that antireflection character and downward conversion character.
According to some embodiments of the present invention, provide a kind of photoelectric device.This device comprises substrate, be arranged on the sandwich construction on the substrate and be arranged on nanostructure functional coating on the electromagnetic radiation receiving surface of device.Functional coating is characterised in that antireflection character and downward conversion character.
Description of drawings
When below the reference accompanying drawing is read, describing in detail, can understand these and other feature of the present invention, aspect and advantage better, in the accompanying drawing:
Fig. 1 is the schematic diagram of one embodiment of the invention;
Fig. 2 is the energy diagram of the material relevant with one embodiment of the present of invention;
Fig. 3 is the schematic diagram of another embodiment of the present invention;
Fig. 4 is the schematic diagram of one embodiment of the invention;
Fig. 5 is the schematic diagram of another embodiment of the present invention;
Fig. 6 is the schematic diagram of one embodiment of the invention.
Embodiment
Discuss in detail as institute hereinafter, some embodiments of the present invention provide a kind of coating that is used to improve the optical surface of power conversion.These embodiment advantageously reduce because the light loss that reflection and thermalization mechanism cause.Embodiments of the invention are also described a kind of improved photoelectric device, and the surface of this photoelectric device is provided with such coating.
Such as in entire description and claims use, can use approximate language to modify any quantificational expression that changes allowably, and can not cause the change of the basic function relevant with it.Therefore, use the value of modifying to be not limited to specified exact value such as one or more terms of " (about) approximately ".In some cases, approximate language can be corresponding to the precision of the instrument of measuring this value.
" nanostructure " is to have feature sizes less than about 500 nanometers (nm), less than about 200nm, less than about 100nm, less than about 50nm or even less than at least one zone of about 20nm or the structure of characteristic dimension as used herein.The example of this class formation comprises nano wire, nanometer rods, nanotube, branch shape nanocrystal, nanometer four leg structures (nanotetrapod), three-prong structure (tripod), two corner structures (bipod), nanocrystal, nano dot, nano particle etc.The material character of nanostructure can be a homogeneous basically.But in other embodiments, nanostructure also can be heterogeneous.Nanostructure can be crystal (monocrystal or polycrystal), amorphous or its combination basically.The further feature of nanostructure can have micron or even the interior size of millimeter scope.On the one hand, the size of at least one size of nanostructure is less than about 500nm, for example less than about 200nm, less than about 100nm, less than about 50nm or even less than about 20nm.
Term " functional coating " is meant the coating or the layer of the optical surface that is used to improve power conversion as used herein.
According to the present invention, term " substantial transparent " expression nanostructure allows most of solar radiation to pass.Major part can be at least about 70% solar radiation.
According to the present invention, " perpendicular " expression main shaft is with respect to the angle tilt of about 90 degree of substrate surface Cheng Zaicong to about 75 degree scopes.
According to one embodiment of present invention, provide a kind of article with nanostructure functional coating.Coating is arranged at least one surface of substrate.Coating is characterised in that antireflection character and downward conversion character (down-converting property).
" antireflection character (anti-reflection property) " is meant the character on coating, layer or the surface of the light reflection that reduces optical surface as herein defined.Antireflection character can be depending on various parameters, for example the structure on the thickness of the refractive index of material, layer or layer or surface.
In general, the refractive index of medium is defined as the ratio of the light velocity in the light velocity and the medium in the vacuum.According to the present invention, the refractive index of nanostructure can refer to " effective refractive index ".Effective refractive index is used to determine the phase lag and the decay of coherent wave when the array of the nanostructure of passing substantial transparent is propagated in electromagnetic radiation as herein defined.The optics nanostructure is the composite material type with low-refraction.These composite materials are made up of the air and the basis material of various shares usually.Determine the effective refractive index of nanostructure such as the parameter of size, local volume/area fraction, air/material share and material refractive index.For example, the argumentation of the effective refractive index of the suspended substance of relevant sub-wavelength scattering particles is described in people's such as A.Reyes-Coronado " Measurementof the Effective Refractive Index of a Turbid Colloidal Suspension UsingLight Refraction " (New Journal of Physics 7 (2005) 89), and this article is incorporated into this paper by reference.
According to one embodiment of present invention, functional coating can comprise anti-reflecting layer." anti-reflecting layer " can be single layer or more than a layer (multilayer) as used herein.
In one embodiment, anti-reflecting layer has consistent refractive index.For the specific wavelength of normal incidence, the reflectance with antireflection array of an induced refractive index can reach minimum value.In alternative, this layer can have graded index (graded refractive index).The gradient of refractive index (gradient) can realize by forming variation or structural change.
Graded index may be defined as along the preferential direction change of refractive.Change of refractive can be continuously or gradually along preferential direction.Be characterised in that the anti-reflecting layer that graded index distributes provides omnidirectional, broadband antireflective properties.
In certain embodiments, anti-reflecting layer can comprise the array of nanostructure.The layer that comprises nanostructure has the refractive index of the refractive index that is lower than dense material usually owing to the nanoporous of this layer.Nanostructure can be substantially perpendicular to substrate, or with respect to the angled inclination of substrate.Nanostructure can be arranged on the substrate by random fashion or by periodic manner.
The optical property of nanostructure can be determined by its size and chemistry or surface composition.Can utilize the various character such as absorbent properties, emission characteristic and refractive index properties of nanostructure to create can be special and adjust the anti-reflecting layer that is used for various application.
In one embodiment, nanostructure can have along the cross-sectional area of its height basically identical.Cross-sectional area can be a different shape.The example of different shape can include but not limited to circle, triangle, rectangle, square or hexagon.Irregularly shaped also is possible.In one embodiment, all nanostructures are nano wires basically.In another embodiment, all nanostructures are nanometer rods basically.
In above embodiment, the height of nanometer rods can be less than about 100nm.In certain embodiments, the height of nanometer rods can change in about 100nm scope from about 50nm.In addition, nanometer rods can periodically be arranged on the substrate surface, and wherein the cycle is less than the wavelength of electromagnetic radiation.This type of nanometer rods with cross-sectional area of basically identical provides low-down reflectance usually.
In above embodiment, the reflectivity of anti-reflecting layer is characterised in that the sub-wavelength scattering phenomenon.Nanostructure with cross-sectional area of basically identical can show as the sub-wavelength scatterer, the transmittance that the sub-wavelength scatterer provides big forward scattering and arrives the bottom substrate subsequently.In absorbing silicon nanowire array, show this effect.(still, under the sort of situation, absorb nano wire owing to use, can take place owing to light is caught the strong absorption that causes, " Strong Broadband Optical Absorption in Si NanowireFilms " (Journal of Nanophotonics as people such as for example L.Tsakalakos, 17July 2007, Vol.l) described in, this article is incorporated into this paper by reference).When light and the interaction of sub-wavelength cylindrical object, light is followed Rayleigh criterion and " Mie scattering (Mie scatter) " is taken place, so that the biquadratic of scattering cross section and particle size proportional (for example, under the situation of spheroidal particle).This phenomenon is described at people such as for example C.F.Bohren " Absorption and Scattering of Light bySmall Particles " (Wiley-Interscience, New York (1983)), and this article is incorporated into this paper by reference.
In another embodiment, the array of nanostructure can have graded index.In certain embodiments, graded index is to cause owing to the main shaft along nanostructure has inconsistent cross-sectional area.In other words, nanostructure can have the gradual change cross-sectional area along main shaft.Main shaft is substantially perpendicular to the surface of substrate.In this embodiment, nanostructure of the present invention can have different shape.In one embodiment, the shape of all nanostructures is pyramids basically.Perhaps, the shape of all nanostructures is conical basically.
Here the term of mentioning " pyramid " generally is meant the geometry definition of this term.Pyramid is the polyhedron that forms by connection polygon bottom surface and the point that is called the summit.Every base and summit form a triangle.It can be considered to have the cone of polygon bottom surface.Shapes such as triangle, square, pentagon, hexagon can be adopted in the polygon bottom surface.Pyramid also can have the star polygon bottom surface." coniform shape " of this paper definition is meant that with planar bottom surface and surface (side surface) be the figure on boundary, wherein should be formed by the track that the summit is attached to all straightways of bottom surface circumference on the surface.The axle of cone is the straight line through the summit, and side surface has rotational symmetry around this axle.The bottom surface can be circular or oval, and the summit can be positioned at any position.For example, cone can be upright cone or inclination cone.
As mentioned above, pyramid or conical nanostructure have the continually varying cross-sectional area along main shaft usually.The volume fraction of nanostructure changes with cross-section variation.Along with the variation of volume fraction, air also changes along main shaft with the ratio of material.Discuss as mentioned, this produces the variation of effective refractive index along the main shaft of nanostructure, and causes gradual change effective refractive index nanostructure.This anti-reflecting layer is described in the patent application of submitting on April 9th, 2009 (application number 12/421101) that is entitled as " NanostructuredAnti-reflection Coatings and Associated Methods and Devices ", and this application is incorporated into this paper by reference.
The interior angle that depends on pyramid or coniform shape, but nanostructure relative narrower or broad.Interior angle used herein can define with reference to Fig. 1.Fig. 1 illustrate be positioned at the surface on 102 single pyramid or cross section Figure 100 of conical nanostructure.This nanostructure has main shaft 104, and 106 is the straight lines that the circumference of bottom surface are attached to the summit.Interior angle is the angle 110 between axle 104 and the straight line 106.
Depend on interior angle, each pyramid or conical nanostructure can have precipitous or mild gradual change.The gradient of refractive index depends on the interior angle of nanostructure.The interior angle of pyramid or conical nanostructure can be greater than about 1 degree.In one embodiment, interior angle can from about 1 spend about 20 the degree, from about 20 spend about 40 the degree, from about 40 spend about 60 the degree or from about 60 spend about 70 the degree scopes in.In preferred specific embodiments of final use for some, interior angle can spent in the scopes of about 40 degree from about 20.
Functional coating can have lower zone and upper area.Lower zone contacts with substrate usually, and upper area is relative with lower zone basically.The refractive index of coating can be gradually varied to the value of upper area from the value of lower zone.Because lower zone contacts with substrate, so lower zone has the value of mating substantially with the refractive index of substrate usually.The type of Qu Yu variations in refractive index can be depending near the existence of upper area " medium " upward, and this will discuss hereinafter.In certain embodiments, refractive index can increase or reduce along the direction of extending from the lower zone to the upper area, and mates substantially with near the refractive index of medium the upper area.
In one embodiment, medium can be air (refractive index equals 1 substantially).Therefore, the refractive index of coating can be according to making the mode than low value that obtains upper area reduce from the lower zone to the upper area.In a particular embodiment, the refractive index of upper area is about 1 than low value.
In certain embodiments, functional coating can comprise a plurality of anti-reflecting layers.It should be noted that described a plurality of layers feature is graded index usually.A plurality of layers with refractive index of variation can deposit on stacked one deck ground, to obtain the gradual change of expectation.In other words, coating can comprise that a plurality of nano-structure arrays are to realize the graded index from the substrate to the surrounding medium.For example, the TiO that has by glancing angle deposition method deposition 2And SiO 2The gradual change effective refractive index coating of nanostructured layers can have from 2.7 and changes to 1.05 refractive index, " OpticalThin-Film Materials With Low Refractive Index For BroadbandElimination Of Fresnel Reflection " (Nature Photonics as people such as J.-Q.Xi, Vol.l, page 176,2007) describe, this article is incorporated into this paper by reference.And, can utilize the combination of nanostructured layers to realize any refractive index value between about 2.7 and about 1.05.
According to some embodiments of the present invention, anti-reflecting layer comprises the gradual change composition (graded composition) from the lower zone to the upper area.Gradual change is formed provides graded index to coating.In other words, because the composition of material changes, so refractive index also changes." gradual change composition " is meant along gradually changing that a direction is formed as herein defined, but gradual change may be always not constant.
Compare with the embodiment that comprises a plurality of anti-reflecting layers, in above embodiment, coating can comprise single anti-reflecting layer.In one embodiment, the combination that can comprise at least two kinds of electric conducting materials is formed in gradual change.The concentration of constituent material gradually changes to realize gradual change.Gradual change in the single layer can realize by the composition of deposition varied concentration.In another embodiment, gradual change is formed and can be realized by depositing multiple material, and wherein every kind of material has the selected composition of the composition that is different from least a other material.Perhaps, the gradual change in the antireflecting coating can have different a plurality of layers of forming by deposition and obtains.
Temperature when size of nanostructure (height and cross sectional dimensions) and shape can be depending on the technology of these nanostructures that are used to grow and growth of nanostructures.In one embodiment, all nanostructures basically of above-mentioned anti-reflecting layer can have the height in from about 100 nanometers to about 10 micrometer ranges.In some preferred embodiments, each nanostructure can have the height in from about 200 nanometers to about 2 micrometer ranges.In one embodiment, each nanostructure can have from about 100nm 2To about 10 4Nm 2Surperficial contact area in the scope.The surface contact area is the cross-sectional area of the lower zone of nanostructure.In certain embodiments, the height of nanostructure and surperficial contact area can change in array.
According to one embodiment of present invention, anti-reflecting layer comprises transparent conductive material.Some examples of suitable transparent conductive material can comprise oxide, sulfide, phosphide, tellurides or its combination.These transparent conductive materials can be through overdopings or are not mixed.In an one exemplary embodiment, conductive oxide can comprise titanium dioxide, silica, zinc oxide, tin oxide, aluminium-doped zinc oxide, fluorine-doped tin oxide, stannic acid cadmium (tin oxide) and zinc (tin oxide).In another embodiment, conductive oxide comprises and contains indium oxide.Suitable some examples that contain indium oxide are tin indium oxide (ITO), Ga-In-Sn-O, Zn-In-Sn-O, Ga-In-O, Zn-In-O and combination thereof.Suitable sulfide can comprise cadmium sulfide, indium sulfide etc.Suitable phosphide can comprise indium phosphide, gallium phosphide etc.In one embodiment, transparent conductive material can have the band gap greater than about 2.0eV.In certain embodiments, anti-reflecting layer can gradual change on forming, and, comprises the transparent conductive material that two or more has the concentration that gradually changes that is.
In certain embodiments, anti-reflecting layer can comprise non-conductive, the non-crystalline material such as glass.The limiting examples of glass can comprise soda-lime glass, alumina silicate glass (alumino-silicateglass), borosilicate glass (boro-silicate glass), silica, rich iron glass.In certain embodiments, the array of the nanostructure of substantially transparent can comprise non-conductive crystalline material.
According to one embodiment of present invention, substrate can have the surface of substantially flat." surface of substantially flat " typically refers to basic even curface as herein defined.The surface can be smooth, but it also can comprise texture (for example, roughness), zigzag and the various scrambling of slight (for example, about 20% of total surface area) relatively.In certain embodiments, substrate can show pliability.In addition, in certain embodiments, the surface of substrate can be curved, has big relatively radius of curvature usually.
Substrate selects to comprise the substrate of any suitable material, and suitable material includes but not limited to metal, semiconductor, doped semiconductor, amorphous dielectric, crystal current medium and combination thereof.In certain embodiments, substrate comprises the material of transparent and electrically conductive as mentioned above.
According to one embodiment of present invention, functional coating is characterised in that downward conversion character." conversion downwards " represents that each incident high-energy photon generates the method for a plurality of electron-hole pairs, and it can be used for reducing the thermalization loss.To down-converter/downward transition material the band-gap energy n incident photon doubly that energy surpasses device material is transformed to n lower energy photon, these lower energy photons are used in and generate " n " individual electron-hole pair in the device.
" downwards conversion " be can in material comprises, ask energy state maybe can with the time material character realized.This material can be transformed to the incident high-energy photon one or more lower energy photons.A preferred embodiment is photon of photo emissions of every absorption.Fig. 2 illustrates this atomic energy level in the downward transition material, and it has illustrated the downward transfer process that wherein produces a lower energy photon.
According to one embodiment of present invention, transition material comprises material of main part and dopant downwards.Material of main part can be used as the optical absorption main body and describes, and it absorbs the incident radiation such as outside photon.Dopant increases the expectation energy level of the inside photon that preferential emission generated based on basic absorbent character.Therefore, in basic aspect, transition material comprises absorbent and cast charge downwards.
Expectation energy level based on light emitted son uses various dopants.In one embodiment, can be used for 1 pair 1 dopant ion of changing downwards and comprise lanthanide ion, transition metal ions and rare earth ion.The example of suitable dopant ion has Ce 3+, Eu 2+, Sm 2+, Cr 3+, Mn 2+And Mn 4+In addition, also sensitizer can be doped in the material of main part with dopant.If owing to for example forbidden transition causes encouraging dopant ion, then sensitizer can be used.Excitation energy is absorbed by sensitizer, sends dopant ion subsequently to.For example, transition metal ions can come sensitization by lanthanide ion.
Launch a photon although Fig. 2 illustrates owing to absorbing the higher-energy photon, it also is possible that photon of every absorption produces a plurality of photons.In certain embodiments, photo emissions of every absorption is more than a photon.Such downward conversion is commonly referred to " quantum-cutting " or " quantum division ".For example, such as pr 3+, Tm 3+Or Gd 3+Single dopant ion or such as Gd 3+-Eu 3+The combination of two ions of double ion can generate two lower energy photons for each incident high-energy photon.Other combination comprises Yb 3+-Tb 3+And Yb 3+-pr 3+Double ion.
In certain embodiments, transition material can comprise organic material downwards.For example, organic downward transition material can include organic dye, as BASF lumogen dyestuff.In addition, other downward transition material can comprise the organic-inorganic dyestuff of mixing.
According to one embodiment of present invention, the form that downwards transition material can nanostructure exists.Discuss as mentioned, nanostructure can be different shape and size.Downwards transition material also can comprise extra layer on them, so that carry out surface passivation (for example, nucleocapsid structure), or is beneficial to and is incorporated into functional coating (for example, silica or organic monolayer shell).
The optical property of nanostructure is can be on very most of definite by its size and chemistry or surface composition.By the size and the composition of the used in the present invention nanostructure of control, the nanostructure of transition material can absorb the radiation of specific wavelength or particular range of wavelengths downwards, and not scattering.Nanostructure can absorb from UV to the visible light to near-infrared to infrared radiation.In the preferred embodiment of solar energy converting, nanostructure absorbs the radiation that is lower than about 550nm, and the radiation of 550nm is longer than in emission.The big I of the nanostructure of Shi Yonging is suitably less than about 500nm in the present invention.In some specific embodiments, the big I of nanostructure from about 10nm in about 100nm scope.
According to one embodiment of present invention, the nanostructure of transition material can be embedded in the anti-reflecting layer downwards.Term " embedding " is used for expression as used herein, and the conversion nano structure is enclosed in the anti-reflection nano-metric structure at least basically downwards.Represented this class embodiment among Fig. 3, Fig. 3 illustrates the cross-sectional view of article 300, and wherein anti-reflecting layer 301 is arranged on the surface 303 of substrate 302.Anti-reflecting layer 301 comprises the array 304 of nanostructure 306.Conversion nano structure 310 (that is the nanostructure that is formed by downward transition material) is embedded in basic all nanostructures 306 of array 304 downwards.
In another embodiment, downward conversion nano structure can be arranged on the below of anti-reflecting layer.Fig. 4 illustrates the cross-sectional view of article 400.Anti-reflecting layer 401 is arranged on the surface 403 of substrate 402.Anti-reflecting layer comprises the array 404 of anti-reflection nano-metric structure 406, and it has lower zone 408.Conversion nano structure 410 (that is the nanostructure of downward transition material) contacts with the lower zone 408 of anti-reflection nano-metric structure 406 and surface 403 essence of substrate downwards.
Fig. 5 illustrates the cross-sectional view of the article 500 of another embodiment of the present invention.Anti-reflecting layer 501 is arranged on the surface 503 of substrate 502.Anti-reflecting layer has the array 504 of nanostructure 506.Nanostructure 506 separates each other, and forms space 508 between nanostructure 506.Conversion nano structure 510 (that is the nanostructure of downward transition material) is arranged in basic all spaces 508 of antireflection array 504 downwards.
In some embodiments of the invention, transition material can be present in the functional coating according to any amount (percentage) that is suitable for desired function downwards.Suitably, depend on the type of application, antireflecting coating and the type of downward transition material, by volume calculate that transition material can be present in the functional coating by the rank between about 0.001% to about 80% downwards.In some preferred embodiments, percentage (amount) can from about 20% in about 50% scope.In above embodiment, the conversion nano structure is evenly distributed in the functional coating usually downwards.Perhaps, but the nanostructure random distribution.In certain embodiments, nanostructure forms the density gradient from the lower zone to the upper area in functional coating.
With functional coating wherein comprise anti-reflecting layer before the embodiment that describes compare, in another embodiment of the present invention, functional coating comprises downward transition material layer.In this embodiment, transition material exists with crystal form downwards.Transition material can be monocrystal or polycrystal (polycrystalline/multi-crystalline) downwards.Fig. 6 illustrates the article 600 that comprise functional coating 601, and in this embodiment of the present invention, transition material layer 604 is arranged on the surface of substrate 602 downwards.Array 606 by nanostructure 608 makes downward conversion layer 604 have antireflection character.The array 606 of nanostructure 608 helps low reflectance.The array 606 of nanostructure 608 (it constitutes conversion " layer " downwards) is formed by aforesaid downward transition material.
In one embodiment, nanostructure 608 has consistent cross-sectional area along main shaft usually.Main shaft is substantially perpendicular to the surface of substrate.The size of nanostructure (height and diameter) is through selecting to realize low reflectance by the sub-wavelength scattering phenomenon in the conversion layer downwards.In another embodiment, the nanostructure 608 of array 606 has inconsistent cross-sectional area along the main shaft of nanostructure.In other words, nanostructure can have the gradual change cross-sectional area along main shaft, and this causes the graded index of functional coating.In this embodiment, nanostructure of the present invention can have different shape.In one embodiment, the shape of all nanostructures is pyramids basically.Perhaps, the shape of all nanostructures is conical basically.
Another embodiment of the present invention relates to a kind of photoelectric device.This device comprises substrate and the sandwich construction that is arranged on the substrate.This device also comprises the nanostructure functional coating on the electromagnetic radiation receiving plane that is arranged on device.Functional coating is characterised in that antireflection character and downward conversion character.The group that the optional free PN junction of the sandwich construction of device, heterojunction, quantum well and superlattice are formed.In one embodiment, functional coating is arranged on arbitrary of substrate.In another embodiment, functional coating is arranged on the optical receiving surface of sandwich construction.
" photoelectric device " is meant and produces light or make the device of using up in its operation as used herein.Photoelectric device is electrical-optical or light-electric device or the instrument that uses this class device in its operation.Usually, semiconductor junction is the part of photoelectric device.Semiconductor junction can be p-n junction, n-p knot, p-i-n knot or n-i-p knot.For example, as understood by the skilled person, p-n junction can generate electric energy existing under the situation of daylight, and this is the basis of the general operation of photovoltaic device or solar cell.This device comprises that also the electric energy that is used for being generated guides the conduction path to external circuit.
In addition, photoelectric device can be a several types.In certain embodiments, photoelectric device can be photodiode, light-emitting diode, photovoltaic device or semiconductor laser.These photoelectric devices can be used for various application.Application example comprises electronic console, photodetector, general lighting, camera and optical fiber communication.
In a preferred embodiment, photoelectric device is photovoltaic cell or photovoltaic module.Photovoltaic module can have the array of photovoltaic cell.Photovoltaic module can have the cloche that is used to protect battery, and functional coating is arranged on this cloche.Functional coating can be arranged on photovoltaic cell or the photovoltaic module so that functional coating is exposed to solar radiation.In certain embodiments, functional coating is arranged on the back side of module cloche.This coating can be arranged on photovoltaic module more than on the position.For example, coating can be arranged on the surface of the back side of end face, module cloche of module cloche and/or the solar cell in the module, so that coating is exposed to solar radiation.
In certain embodiments, photovoltaic module or photovoltaic cell can include but not limited to amorphous silicon battery, crystal silicon cell, mixing/heterojunction amorphous and crystal silicon cell, CdTe hull cell, crystallite lamination (micromorph tandem) silicon thin-film battery, Cu (In, Ga) Se 2(CIGS) hull cell, GaAs battery, multijunction solar cell, DSSC based on III-V family or solid-state organic/polymer solar battery.In certain embodiments, solar cell can comprise transparent conductor, and the function antireflecting coating is set on this transparent conductor.
The nanostructure functional coating can be by forming (deposition) such as various technology such as Wet-type etching, dry-etching, physical vapour deposition (PVD), sputter, solution growth and solution depositions.The example of suitable dry-etching technology includes but not limited to reactive ion etching (RIE), inductively coupled plasma (ICP) etching and combination thereof.The dry-etching technology can combine with the method that forms the nano etched mask.The nano etched mask can form by nanosphere photoetching, dip-coating, spraying, spin coating, sputter, in-situ nano particle deposition and combination thereof.The example of suitable Wet-type etching technology is the auxiliary Wet-type etching of metal.
In an one exemplary embodiment, deposition technique is selected from the group of being made up of chemical vapour deposition (CVD), wet chemical solution deposition, physical vapour deposition (PVD) and glancing angle deposition.It is known that glancing angle is deposited on this area, and it is at " Designing Nanostructures byGlancing Angle Deposition " (Proceedings of SIPE Vol.5219Nanotubesand Nanowires of people such as for example Y.P.Zhao; SPIE, Bellingham, WA, 2003) in be described.Briefly, glancing angle deposition (GLAD) technology is normally undertaken by glancing angle deposition is combined with substrate location control.GLAD comprises processes of physical vapor deposition, wherein in substrate rotation, the deposition flow with respect to surface normal become one than wide-angle incide on the substrate.GLAD produces column structure by capture-effect in thin film growth process, and the shape of substrate Spin Control pillar.GLAD provides three parameters, that is, incidence angle, growth rate and substrate rotary speed are so that the form of control nanostructure.In the GLAD process, deposition rate not only has vertical component (with respect to substrate), but also has cross stream component.Cross growth speed helps capture-effect, and this causes two major advantages to GLAD: self alignment effect and horizontal engraving effect.
Example
Provide following example so that further specify some embodiment of the present invention.These examples should not be read as and limit the present invention by any way.
Example 1
In an example, the nanosphere photoetching combines with reactive ion etching (RIE) to form the nanostructure anti-reflecting layer on glass substrate.The nanosphere photoetching is well-known, it is described in " Nanosphere Lithography:A Materials GeneralFabrication Process For Periodic Particle Array Surfaces " (J.Vac.Sci.Technol.A, 131553 (1995)) of people such as for example J.C.Hulteen.By the amorphous silica layer coating fused silica substrate of high-temperature low-pressure chemical vapour deposition technique (in some cases, by other method) with 1 micron thickness.After the standard clean process, by being immersed in, substrate carries out the nanosphere photoetching in the solution that comprises the pipe/polyhenylethylene nano ball, so that when shifting out from solution, nanosphere is assembled into hexagon solid matter individual layer dot matrix on glass surface.Then, with 100nm Ni film electron beam evaporation to sample, so that the position below the gap that is being arranged in nanosphere on the glass substrate forms Ni nanoscale point/triangle.Lift to remove nanosphere by being immersed in the acetone allowing from the surface.By sample being placed in the RIE reactor, utilizing standard oxide etch recipe, 2 microns etch depths of aligning to form nano-structure array.Higher-wattage in the RIE reactor causes with respect to glass substrate etching Ni more, and this causes conical nanostructure.By the etch-rate with respect to Ni nanoscale point/leg-of-mutton etch-rate of control glass substrate, create narrow or wide conical nanostructure.At last, utilization comes etching Ni for this metal 100% overetched standard etchant of Ni.Then, by dip-coating, spraying or spin-coating method downward conversion nanoparticles is placed on the surface of cylindrical or conical nanostructure.
Example 2
The silicon oxide film that will comprise downward conversion particles, or deposits on the solar cell on glass substrate from the spin-coating glass solution deposition.By mixing downward conversion nanoparticles is incorporated in the film with the spin-coating glass precursor aqueous solution.Laminated film is carried out thermal annealing to solidify the silica phase.By being immersed in, substrate carries out the nanosphere photoetching in the solution that comprises the pipe/polyhenylethylene nano ball, so that when when solution shifts out, nanosphere is assembled into hexagon solid matter individual layer dot matrix on glass surface.Then, with 100nm Ni film electron beam evaporation to sample, so that in the position below the nanosphere gap on the glass substrate, form Ni nanoscale point/triangle.Lift to remove nanosphere by being immersed in the acetone allowing from the surface.By sample being placed in the RIE reactor, utilizing standard oxide etch recipe, 2 microns etch depths of aligning to form nano-structure array.By the etch-rate with respect to Ni nanoscale point/leg-of-mutton etch-rate of control glass substrate, create narrow or wide conical nanostructure.
Example 3
Form the monocrystal of downward transition material by the standard crystal growing method.Then, crystal is thinned to the expectation rank and carries out etching, to form the array of nanostructure by said method.
Example 4
By utilizing CVD, MOCVD and correlation technique the downward transition material of gas phase direct growth, perhaps utilize catalytic solution known in the art to decompose and growing method is come from the solution downward transition material of direct growth mutually from the nanostructure form.
Can utilize binder layer that nanostructure functional coating and PV module are integrated such as the index-matched of EVA (ethylene-vinyl alcohol).
Although this paper only illustrates and described some feature of the present invention, those skilled in the art can associate many modifications and change.Therefore, will understand, the claims of enclosing will be contained all such modifications and the change that drops in the true scope of the present invention.
The element tabulation
The cross-sectional view of 100 single pyramids or conical nanostructured
102 surfaces
104 main shafts
106 circumferences with the bottom surface are attached to the straight line on summit
Angle between 110 axles 104 and the straight line 106
The cross-sectional view of 300 article
301 anti-reflecting layers
302 substrates
304 arrays
306 nanostructures
310 downward conversion nano structures
The cross-sectional view of 400 article
401 anti-reflecting layers
402 substrates
403 surfaces
The array of 404 anti-reflection nano-metric structures
406 anti-reflection nano-metric structures
408 lower zones
410 downward conversion nano structures
The cross-sectional view of 500 article
501 anti-reflecting layers
502 substrates
The array of 504 anti-reflection nano-metric structures
506 anti-reflection nano-metric structures
Space between 508 nanostructures
510 downward conversion nano structures
600 article
601 functional coatings
602 substrates
604 downward transition material layer
The array of 606 anti-reflection nano-metric structures
608 nanostructures.

Claims (10)

1. article comprise:
Be arranged on the nanostructure functional coating on the substrate, wherein said coating is characterised in that antireflection character and downward conversion character.
2. article as claimed in claim 1, wherein said nanostructure functional coating comprises the anti-reflecting layer of the array that comprises nanostructure.
3. article as claimed in claim 2, wherein said anti-reflecting layer has the refractive index of unanimity or gradual change.
4. article as claimed in claim 1, wherein said nanostructure functional coating comprises downward transition material.
5. article as claimed in claim 4, wherein said nanostructure functional coating comprises anti-reflecting layer, and the nanostructure of described downward transition material is embedded in the described anti-reflecting layer.
6. article as claimed in claim 4, wherein said nanostructure functional coating comprises anti-reflecting layer, and the nanostructure of described downward transition material is arranged on the below of described anti-reflecting layer.
7. article as claimed in claim 4, described nanostructure in the wherein said anti-reflecting layer separates each other so that form the space in the array of described nanostructure, and downward conversion nano structure is arranged in all spaces basically of the array of described nanostructure.
8. article as claimed in claim 4, wherein said downward transition material exists with crystal form.
9. article as claimed in claim 8, wherein said downward transition material comprises the array of nanostructure, and each nanostructure has the cross-sectional area of basically identical or gradual change.
10. photoelectric device comprises:
Substrate;
Be arranged on the sandwich construction on the described substrate; And
Be arranged on the nanostructure functional coating on the electromagnetic radiation receiving surface of described device, wherein said nanostructure functional coating is characterised in that antireflection character and conversion character downwards.
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